Durable miniature gas composition detector having fast response time

ABSTRACT

A miniature oxygen sensor makes use of paramagnetic properties of oxygen gas to provide a fast response time, low power consumption, improved accuracy and sensitivity, and superior durability. The miniature oxygen sensor disclosed maintains a sample of ambient air within a micro-channel formed in a semiconductor substrate. O 2  molecules segregate in response to an applied magnetic field, thereby establishing a measureable Hall voltage. Oxygen present in the sample of ambient air can be deduced from a change in Hall voltage with variation in the applied magnetic field. The magnetic field can be applied either by an external magnet or by a thin film magnet integrated into a gas sensing cavity within the micro-channel. A differential sensor further includes a reference element containing an unmagnetized control sample. The miniature oxygen sensor is suitable for use as a real-time air quality monitor in consumer products such as smart phones.

BACKGROUND

1. Technical Field

The present disclosure relates to the fabrication of microelectronicenvironmental sensors, such as gas composition sensors.

2. Description of the Related Art

Oxygen is one of the most important and abundant chemical species. Itconstitutes 21% of the earth's atmosphere, and is needed to sustainplant and animal life. Oxygen is also widely employed for industrialpurposes. Conventional oxygen sensors are widely used in laboratory andindustrial applications, wherever oxygen is consumed, emitted, orotherwise present. Such oxygen sensors, for example, those shown inFIGS. 2 and 3 below, generally have large scale form factors, tend to beexpensive, and typically require involvement of skilled operators.

With the advent of micro-mechanical systems, deployment of sensors andfeedback control systems in smaller scale applications is made possible.For instance, many electronic devices now contain environmental sensors.In one example, electronic thermostats connected to climate controlsystems rely on temperature sensors to trigger activation of furnacesand air conditioners. In another example, electronic weather stationsrely on internal temperature sensors, barometric pressure sensors, andhumidity sensors. Small scale consumer products such as motion activatedair fresheners can make use of sensors that detect changes in ambientlight, or changes in air flow.

Miniature sensors that are typically embedded on board mobile computingdevices such as smart phones include, for example, magnetic fieldsensors used to determine orientation of the smart phone relative to theearth's magnetic field. Providing additional environmental sensorswithin smart phones, tablet computers, and the like may encourageprogram developers to create applications that otherwise might not bepossible. In particular, if miniaturized gas sensors could be providedin consumer products, they might find wide use for medical applicationssuch as pulmonary monitoring.

BRIEF SUMMARY

A miniature gas sensor leverages paramagnetic properties of oxygen gasto measure a Hall voltage induced by gas molecule segregation in anapplied magnetic field. Certain atoms, including oxygen, have a netmagnetic dipole moment that tends to align in an external magneticfield. While such paramagnetic effects can be canceled out by collisionson a macroscopic scale, they can be sustained more easily across smalldistances that exist within microelectronic devices.

The miniature sensor described can be implemented to detect gases otherthan oxygen, provided the subject gas also exhibits paramagnetism oranother property that can be similarly manipulated.

The miniature oxygen sensor disclosed maintains a sample of ambient airwithin a micro-channel formed in a semiconductor substrate. Themicro-channel contains a constant volume of O₂ gas. When subjected to amagnetic field, the O₂ molecules align with the magnetic field andsegregate, thereby establishing a measureable Hall voltage. Aconcentration of oxygen present in the sample of ambient air can bededuced from a change in Hall voltage in response to at least amomentary variation in the applied magnetic field. The magnetic fieldcan be applied either by an external magnet or by a thin film magnetthat is integrated into the micro-channel.

A differential sensor further includes a second micro-channel containinga control sample to which a magnetic field is not applied. Comparison ofthe Hall voltage measurement and a control measurement yields adifferential Hall voltage measurement having improved accuracy.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

In the drawings, identical reference numbers identify similar elements.The sizes and relative positions of elements in the drawings are notnecessarily drawn to scale.

FIG. 1 is a screen shot of a smart phone running a weather stationapplication that displays data from an on-board miniature oxygen gasmicro-sensor.

FIG. 2 is a tree diagram showing different types of existing oxygen gasdetection devices.

FIG. 3 is a schematic diagram of a conventional macro-scale mechanicalgas detection system.

FIG. 4A is a schematic diagram of a prior art electrical circuit for usein implementing a Hall effect sensor.

FIG. 4B is a plot of Hall voltage measured in response to an appliedmagnetic field for the Hall effect sensor shown in FIG. 4A.

FIG. 5 is a cross section of a prior art integrated circuitimplementation of a Hall effect sensor that may be used in theelectrical circuit shown in FIG. 4A.

FIGS. 6A-6C are cross sections along a cut line A-A′ (shown in FIG. 7)of an oxygen gas micro-sensor having an external magnet, as describedherein.

FIG. 7 is a top plan view of a differential oxygen gas micro-sensor(left) and a reference sensor (right) as described herein.

FIG. 8 is a plot of differential output voltage as a function ofmagnetic field strength for three different gas concentrations, asmeasured by a gas micro-sensor that uses the Hall effect.

FIG. 9A is a reproduction of the cross section shown in FIG. 6A, inwhich an external magnet is used to magnetize a gas sensing cavity.

FIG. 9B is a cross-sectional view of a micro-sensor in which anintegrated magnetic thin film is used to magnetize a gas sensing cavity.

FIGS. 10A and 10B are top plan views of an oxygen gas micro-sensor(left) that uses an external magnet, and a similar micro-sensor havingan integrated thin film magnet (right).

FIGS. 11A-11C are cross-sectional views of an oxygen gas micro-sensorthat includes an integrated magnetic thin film, as described herein.

FIG. 12 is a flow diagram showing a sequence of processing steps in amethod of fabricating a gas micro-sensor as described herein.

DETAILED DESCRIPTION

It will be appreciated that, although specific embodiments of thepresent disclosure are described herein for purposes of illustration,various modifications may be made without departing from the spirit andscope of the present disclosure. Accordingly, the present disclosure isnot limited except as by the appended claims.

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various aspects of thedisclosed subject matter. However, the disclosed subject matter may bepracticed without these specific details. In some instances, well-knownstructures and methods of semiconductor processing comprisingembodiments of the subject matter disclosed herein have not beendescribed in detail to avoid obscuring the descriptions of other aspectsof the present disclosure.

Unless the context requires otherwise, throughout the specification andclaims that follow, the word “comprise” and variations thereof, such as“comprises” and “comprising” are to be construed in an open, inclusivesense, that is, as “including, but not limited to.”

Reference throughout the specification to “one embodiment” or “anembodiment” means that a particular feature, structure, orcharacteristic described in connection with the embodiment is includedin at least one embodiment. Thus, the appearance of the phrases “in oneembodiment” or “in an embodiment” in various places throughout thespecification are not necessarily all referring to the same aspect.Furthermore, the particular features, structures, or characteristics maybe combined in any suitable manner in one or more aspects of the presentdisclosure.

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various aspects of thedisclosed subject matter. However, the disclosed subject matter may bepracticed without these specific details. In some instances, well-knownstructures and methods of semiconductor processing comprisingembodiments of the subject matter disclosed herein have not beendescribed in detail to avoid obscuring the descriptions of other aspectsof the present disclosure.

Unless the context requires otherwise, throughout the specification andclaims that follow, the word “comprise” and variations thereof, such as“comprises” and “comprising” are to be construed in an open, inclusivesense, that is, as “including, but not limited to.”

Reference throughout the specification to insulating materials orsemiconducting materials can include various materials other than thoseused to illustrate specific embodiments of the transistor devicespresented. The term “epitaxial silicon compounds” should not beconstrued narrowly to limit an epitaxially grown structure to Si orSiGe, for example, but rather, the term “epitaxial silicon compounds” isbroadly construed to cover any compounds that can be grown epitaxiallyfrom a crystalline silicon surface.

Reference throughout the specification to conventional thin filmdeposition techniques for depositing silicon nitride, silicon dioxide,metals, or similar materials include such processes as chemical vapordeposition (CVD), low-pressure chemical vapor deposition (LPCVD), metalorganic chemical vapor deposition (MOCVD), plasma-enhanced chemicalvapor deposition (PECVD), plasma vapor deposition (PVD), atomic layerdeposition (ALD), molecular beam epitaxy (MBE), electroplating,electro-less plating, and the like. Specific embodiments are describedherein with reference to examples of such processes. However, thepresent disclosure and the reference to certain deposition techniquesshould not be limited to those described. For example, in somecircumstances, a description that references CVD may alternatively bedone using PVD, or a description that specifies electroplating mayalternatively be accomplished using electro-less plating. Furthermore,reference to conventional techniques of thin film formation may includegrowing a film in situ. For example, in some embodiments, controlledgrowth of an oxide to a desired thickness can be achieved by exposing asilicon surface to oxygen gas or to moisture in a heated chamber.

Reference throughout the specification to conventional photolithographytechniques, known in the art of semiconductor fabrication for patterningvarious thin films, includes a spin-expose-develop process sequenceinvolving a photoresist. Such a photolithography sequence entailsspinning on the photoresist, exposing areas of the photoresist toultraviolet light through a patterned mask, and developing away exposed(or alternatively, unexposed) areas of the photoresist, therebytransferring a positive or negative mask pattern to the photoresist. Thephotoresist mask can then be used to etch the mask pattern into one ormore underlying films. Typically, a photoresist mask is effective if thesubsequent etch is relatively shallow, because photoresist is likely tobe consumed during the etch process. Otherwise, the photoresist can beused to pattern a hard mask, which in turn, can be used to pattern athicker underlying film.

Reference throughout the specification to conventional etchingtechniques known in the art of semiconductor fabrication for selectiveremoval of polysilicon, silicon nitride, silicon dioxide, metals,photoresist, polyimide, or similar materials includes such processes aswet chemical etching, reactive ion (plasma) etching (RIE), washing, wetcleaning, pre-cleaning, spray cleaning, chemical-mechanicalplanarization (CMP) and the like. Specific embodiments are describedherein with reference to examples of such processes. However, thepresent disclosure and the reference to certain deposition techniquesshould not be limited to those described. In some instances, two suchtechniques may be interchangeable. For example, stripping photoresistmay entail immersing a sample in a wet chemical bath or, alternatively,spraying wet chemicals directly onto the sample.

Specific embodiments are described herein with reference to examples ofintegrated micro-sensors that have been produced; however, the presentdisclosure and the reference to certain materials, dimensions, and thedetails and ordering of processing steps are exemplary and should not belimited to those shown.

In the figures, identical reference numbers identify similar features orelements. The sizes and relative positions of the features in thefigures are not necessarily drawn to scale.

FIG. 1 shows a smart phone 1 equipped with a miniature magneticfield-based gas sensor configured as an oxygen detector that can be usedto monitor ambient air quality in real time. The miniature gas sensor,as described below, is designed to have a fast response time, on theorder of milliseconds, about a thousand times faster than conventionalgas concentration sensors. Furthermore, because the miniature gas sensorrelies on a Hall effect sensing element, it consumes very littleelectrical power, making it feasible for deployment on a mobilecomputing device. Because the miniature gas sensor contains no reactingmaterial, it has an essentially indefinite lifetime.

A shell of the smart phone 1 can be modified so as to allow exposure ofthe capacitive sensors to ambient air. An exemplary smart phoneapplication (“app”) can, for example, be programmed to display on thesmart phone screen 2 weather station icons 3. The smart phone app canreport measurements of temperature, relative humidity, pressure, and gasconcentration (e.g., concentration of oxygen molecules O₂) via thereadouts 4, 5, 6, and 7, respectively. The smart phone app can furtherprovide an assessment of air quality 8 based on a comparison of themeasurements to a selected standard. The standard can be pre-programmedor set by a user of the smart phone, for example.

Examples of different types of conventional oxygen gas detectors 10 areshown in FIG. 2. These include near infrared (NIR) photodetectors 12,solid electrolyte detectors 14, optical detectors 16, and semiconductormetal oxide detectors 18.

The NIR photodetector 12 can be used to measure gas absorption uponpassing a NIR laser through oxygen gas.

The solid electrolyte detector 14 detects oxygen gas produced during anelectrolytic chemical reaction, which can be a spontaneous, orpotentiometric reaction 20, or a non-spontaneous, amperiometric reaction22. In a potentiometric reaction 20, a spontaneous current can beproduced by a reaction inside an electrolyte such as Bi₂O₃ or Gd₂O₂doped with CeO₂ or YSZ. In an amperiometric reaction 22, an externalsource of current can drive oxygen from one electrode to another throughthe electrolyte.

Optical detectors 16 operate on the principle that oxygen quenchesluminescence of an organic indicator such as fluoranthane orplatinum-octaethylporphyrin dye.

Semiconductor metal oxide detectors 18 work on the principle thatoxidation of a metal oxide semiconductor produces a change in resistanceof the semiconducting material.

Another type of oxygen gas sensor is a magnetic field-based oxygensensor 24 such as the one shown in FIG. 3. The magnetic field-basedoxygen sensor 24 relies on the paramagnetic property of oxygen gas.Because oxygen is paramagnetic, it can be influenced by magnetic fields.Furthermore, the presence of oxygen within a medium changes the magneticsusceptibility of the medium.

A conventional, macroscopic, magnetic field-based oxygen sensor 24includes a measuring cell 26 in the form of a gas chamber housing amagnet. The magnet has a north pole 28 and a south pole 30 to establisha magnetic field oriented downward along a vertical axis 32. Oxygen gasenters the measuring cell 26 at a gas inlet 34, flows along a gas flowaxis 36 and exits at a gas outlet 38. A dumbbell 39 aligned with the gasflow axis 36 can freely rotate about a spindle 40 in response to theflow of oxygen gas as the gas passes through the measuring cell 26. Aplane mirror 41 can be positioned in the center of the dumbbell 39between the poles of the magnet such that when the dumbbell 39 isdeflected by gas flow, the mirror 41 tilts accordingly. External to themeasuring cell 26, a light source 42 generates a source light beam 44for incidence on the mirror 41. A conventional source light beam 44 maybe, for example, a laser having power in the range of about 1-10 Watts.A reflected light beam 46 can then be detected at a photodetector 48.Signals from both the light source 42 and the photodetector 48 can beenhanced by an amplifier 50 to produce a measurement readout on anindicating unit 51. As long as the flow of oxygen gas through themeasuring cell 26 remains constant, the reflected light beam 46 sensedby the photodetector 48 will also tend to have a constant intensity andbe received at the same angle. However, when a change in the magneticfield strength causes the oxygen flow to vary, the angle of the mirror41 will deflect in response to the change in gas flow. A deflection inthe mirror angle will then cause fluctuation in the reflected light beam46 sensed at the photodetector 48.

FIG. 4A shows a schematic diagram of a Hall circuit 52 for use with ageneric Hall effect sensor. The Hall effect describes a tendency forcharges in a current-carrying wire to drift to one side of the wire whenthe wire is placed in an external magnetic field. This drift is due tothe Lorentz force, F=qv×B. As positive charges drift in one directionand negative charges drift in the opposite direction, a potentialdifference is set up across the wire, orthogonal to the direction ofcurrent flow. Such a potential difference is well known to those ofskill in the art as a Hall potential, or Hall voltage. Hall effectsensors are often used to determine the sign of charge carriers insemiconductor devices, for example, in which both hole currents andelectron currents can exist. In the present context, O₂ gas molecules,having a net dipole moment, can behave like free charges in motion,which causes the molecules to drift in a magnetic field, thus producinga Hall voltage.

The Hall circuit 52 includes a Hall effect sensor 54, a voltageregulator 56, and an operational amplifier (op-amp) 58. A bias voltageV_(input) can be applied through the voltage regulator 56 at a biasvoltage contact 60. The bias voltage can induce a Hall voltage betweenthe terminals 62 and 64 of the Hall effect sensor 54. If the Hallvoltage is then input to the op-amp 58, the Hall voltage can beamplified for ease of monitoring at V_(output).

FIG. 4B shows a switching plot 66 of voltage vs. applied magnetic fieldfor the Hall effect sensor 54 used in a magnetic switch application. Asthe polarity of the applied magnetic field switches through the range ofabout −150 Gauss to +150 Gauss, a Hall voltage rises linearly from about0 V (off state) to about 10 V (on state). Because the Hall voltagearises due to the paramagnetic response of the O₂ gas, the O₂concentration affects the slope 68 of the switching plot 66. As the O₂concentration increases, the slope 68 increases accordingly. At about150 Gauss, the Hall voltage saturates and the slope 68 returns to zero.

FIG. 5 shows a conventional semiconductor implementation of a Halleffect sensor 54 according to one exemplary embodiment. The Hall effectsensor 70 as shown is a four-terminal device having voltage contacts V₁(72), V_(bias) (74), and V₂ (76), and a ground contact (78). Suchvoltage contacts are typically made of a metal (e.g., Al). The V₁voltage contact 72 and the ground contact 78 are coupled to an N+-dopedregion 80 within an epitaxially-grown surface layer 83 in contact with acrystalline silicon substrate 84. Within the surface layer 83 are formedP-N junctions 84 and 86. A downward-directed magnetic field B (88) canbe applied externally as shown. Upon biasing the Hall effect sensor 70by applying a bias voltage between the V_(bias) voltage contact (74) andthe ground contact (78), a current I_(hall) (87) flows and a voltageV_(hall) (82) can be measured between the voltage contacts V₁ (72) andV₂ (76).

FIGS. 6A-6C show a time sequence of snapshots of a miniature magneticfield-based gas sensor 98, according to one embodiment used to carry outa method of detecting a paramagnetic gas. Such a miniature magneticfield-based gas sensor 98 that is appropriate for consumer electronicsdesirably operates at power levels in the range of about 1-10 mW. Thispower range represents about a 1000× power reduction compared to thelarge scale system described above with reference to FIG. 3. Inaddition, it is advantageous for the lifetime of such a miniaturemagnetic field-based gas sensor 98 to exceed that of a conventionalsensor, which typically operates for about 1-5 years. The lifetime ofthe miniature magnetic field-based gas sensor 98 is, in theory,unlimited, because it includes no moving parts and does not consumematerial in chemical reactions. Thus, the miniature magnetic field-basedsensor 98 is more durable than other types of gas sensors.

The miniature magnetic field-based gas sensor 98 includes a gas sensingcavity 100 positioned in an external downward-directed magnetic field88. As shown in FIG. 6A, the gas sensing cavity 100 is empty, prior tointroducing a gas sample. In one embodiment, the gas sensing cavity 100can have the shape of a rhombus having a width of about 50 microns and aheight of about 10 microns. The external downward-directed magneticfield 88 can be supplied by an external permanent magnet having amagnetic north pole 104 and a magnetic south pole 106. The orientationof the external downward-directed magnetic field 88 is indicated byvertical magnetic field lines. The gas sensing cavity 100 can be formedwithin a glass carrier 108, for example, by an oxide etching process,such as a wet etch using a pure, concentrated hydrofluoric acid thatetches glass at a rate of about 15 μm/minute at 50 C. The glass carrier108 can then be inverted and bonded to the crystalline silicon substrate84 in which an integrated Hall effect sensor 70 has been formed. Thecrystalline silicon substrate 84 can have a thickness of, for example,within the range of about 50 microns-150 microns. The glass carrier 108can have a thickness within the range of about 700 microns-1 mm. TheHall effect sensor 70 is designed to make a four-point Hall measurement,e.g., two currents and two voltages. In particular, the Hall effectsensor 70 provides leads to measure the current at the second pad 115and a voltage difference between the first pad sensor contact 114 andthe second sensor contact pad 115. The voltage contacts V₁ (72) and V₂(76) in FIG. 5 are similar to the sensor contact pads 114 and 115,respectively. A volt meter 116 can be used to monitor potentialdifferences ΔV (Hall voltage 82) between the first sensor contact pad114 and the second sensor contact pad 115. Prior to introducing asample, the volt meter 116 may read, for example, 1 mV.

The method of detecting oxygen gas using the magnetic field-based gassensor 98 entails applying a magnetic field to the miniature magneticfield-based gas sensor 98 (FIG. 6A), introducing a gas sample (FIG. 6B),and measuring a Hall voltage indicative of a presence of oxygen in thegas sample (FIG. 6C). As shown in FIG. 6B, when a gas sample containingoxygen molecules 118 (e.g., air) is introduced into the gas sensingcavity 100, initially the volt meter 116 still measures 1 mV. This isbecause the oxygen molecules are still randomly distributed within thesensing cavity 100. Then, because it has the property of paramagnetism,the oxygen gas responds to the applied magnetic field 88 as shown by thesegregation 122 of O₂ molecules in the gas sensing cavity 100. Some ofthe O₂ molecules move toward the magnetic north pole 104, while othersmove toward the magnetic south pole 106, according to the effect of themagnetic field 88 on the dipole moments of the oxygen atoms. As theoxygen gas becomes magnetized, the susceptibility decreases the magneticfield intensity within the gas sensing cavity 100. Segregation 122 ofthe O₂ molecules in the magnetic field 88 thus results in a decrease inthe electric potential difference across the integrated Hall effectsensor 70 as detected by the volt meter 116. After a short timeinterval, the volt meter 116 reads 0.8 mV, indicating development of aHall voltage 82 of 0.2 V across the gas sample, which can be related toan oxygen concentration within the gas sample (FIG. 6C).

The integrated Hall effect sensor 70 used in the present context ishighly sensitive, being capable of detecting a momentary magnetic fieldof a few μTesla. Therefore, it can feature a very fast response time(e.g., milliseconds or microseconds), as compared with a macroscopicconventional oxygen detector (e.g., the one shown in FIG. 3) which istypically capable of sensing magnetic fields of 30-50 mTesla, and has atypical response time of 10 seconds-1 minute.

The miniature magnetic field-based gas sensor 98 may be configured tooperate alongside a control sensor. For example, FIG. 7 shows adifferential micro-structure 126 that senses oxygen gas (O₂) bymeasuring a differential Hall effect. The differential micro-structure126 includes the miniature magnetic field-based gas sensor 98 and areference element 130 that share a common micro-channel 141. The viewsof the miniature magnetic field-based gas sensor 98 shown in FIGS. 6A-6Care cross-sectional views taken along cut line A-A′ of the present viewshown in FIG. 7. The miniature magnetic field-based gas sensor 98 allowsmonitoring of O₂ gas in a sample of ambient air that enters themicro-channel 141 of the differential micro-structure 126 through one ormore openings 136, 138, and 140. The openings 136, 138, and 140 aresized and dimensioned to allow a constant volume of a few microliters ofair to be maintained within the micro-channel 141 which spans both ofthe sensing elements. The openings 136, 138, and 140 can be made, forexample, by drilling. Thus, the reference element 130 is in fluidcommunication with the gas sensing cavity 100 (i.e., the referenceelement contains the same gas as the gas sensing cavity 100). A magneticfield 88 is then applied to the miniature magnetic field-based gassensor 98, in a direction orthogonal to the plane in which the sensorslie, as indicated by the “X.” Meanwhile, no magnetic field is applied tothe reference element 130. In response to the applied magnetic field 88,O₂ molecules in the miniature magnetic field-based gas sensor 98 tend tosegregate, giving rise to a lateral charge separation, whereas O₂segregation does not occur in the reference element 130. The chargeseparation causes an electric potential difference to form between thetwo poles V+ and V−. This potential difference is then measured as thevoltage V_(sensor), for comparison with a reference voltageV_(reference). The voltage differenceΔV _(out) =V _(sensor) −V _(reference)  (1)represents a change in magnetization of the oxygen gas in response tothe applied magnetic field. In general, magnetization M varies with theapplied magnetic field 88 according to the relationshipM=xB,  (2)in which x is proportional to the volume susceptibility of the O₂ gas,the susceptibility being a material constant. The voltage differenceΔV_(out) 144 is thus a differential Hall voltage.

FIG. 8 shows a family of curves 144 of measured values of thedifferential Hall voltage ΔV_(out) (144) as a function of the external,downward-directed magnetic field strength B (88) for three gas samples,each containing a different concentration of O₂. As expected fromequation (2), each of the curves 144 is linear. A gas sample containing1% oxygen produces a linear curve 146; a sample containing 2% oxygenproduces a linear curve 148, and a sample containing 3% oxygen producesa linear curve 150. As the gas concentration increases, the external,downward-directed magnetic field 88 is less effective in segregating theO₂ molecules, so the differential voltage is lower for the same appliedmagnetic field strength.

The side view of the miniature magnetic field-based gas sensor 98 isreproduced in FIG. 9A, for comparison with a corresponding side view ofan alternative oxygen sensor 156 shown in FIG. 9B. The alternativeoxygen sensor 156 features an integrated thin film permanent magnet 158in place of the external permanent magnetic poles 104, 106. Theintegrated thin film permanent magnet 158 may be, for example, anIron-Cobalt-Nickel (FeCoNi) magnet having a thickness of about 1 micron.Such an integrated thin film permanent magnet 158 can be deposited andpatterned after etching the gas sensing cavity 100 from the glasscarrier 108. After the glass carrier 108 is placed over the crystallinesilicon substrate 84, the integrated thin film permanent magnet 158extends downward toward the center of the gas sensing cavity 100.

The top plan view of the miniature magnetic field-based gas sensor 98shown in FIG. 7 is reproduced in FIG. 10A, for comparison with acorresponding top plan view of the alternative oxygen sensor 156 shownin FIG. 10B. The alternative oxygen sensor 156 also includes themicro-channel 141 including the gas inlet opening 136 and the gas outletopening 138. The sensors 98 and 156 function according to the sameprinciples and share substantially the same structure, except for thegeometry of the magnets. Thus, the alternative oxygen sensor 156 is asubstitute for the miniature magnetic field-based gas sensor 98, withthe exception that the alternative oxygen sensor 156 includes the thinfilm permanent magnet 158. It is noted that the thin film permanentmagnet 158 has a smaller size than the external magnet characterized bymagnetic poles 104, 106. Whereas the external downward-directed magneticfield 88 is represented by a large circumscribed “X” in FIG. 10A, thecorresponding thin film magnetic field 162 produced by the thin filmpermanent magnet 158 shown in FIG. 10B is represented by a smallrectangle. However, the size of the magnet itself does not necessarilydictate the strength of the magnetic field produced thereby. Field linesassociated with the external downward-directed magnetic field 88 extendfarther out along the micro-channel 141, whereas field lines produced bythe thin film permanent magnet 158 may tend to be more concentrated inthe region of the gas sensing cavity 100, directly above the sensorcontact pads 114 and 115.

FIGS. 11A-11C show a time sequence of snapshots of the alternativeoxygen sensor 156. The alternative oxygen sensor 156 operates at powerlevels similar to those used for the miniature magnetic field-based gassensor 98. Also, the lifetime of the alternative oxygen sensor 156 iscomparable to the extended lifetime of the miniature magneticfield-based gas sensor 98. The alternative oxygen sensor 156 includesthe gas sensing cavity 100 positioned in the thin film magnetic field162 produced by the thin film permanent magnet 158. As shown in FIG.11A, the gas sensing cavity 100 is empty prior to introducing a gassample. The orientation of the thin film magnetic field 162 is indicatedby vertical magnetic field lines. As described above with reference toFIGS. 6A-6C, the volt meter 116 can be used to monitor potentialdifferences ΔV (Hall voltage 82) between the first sensor contact pad114 and the second sensor contact pad 115. Prior to introducing asample, the volt meter 116 may read, for example, 1 mV.

As shown in FIG. 11B, when a gas sample containing oxygen molecules 164(e.g., air) is introduced into the gas sensing cavity 100, initially thevolt meter 116 still measures 1 mV. This is because the oxygen moleculesare still distributed randomly within the gas sensing cavity 100. Then,because it has the property of paramagnetism, the oxygen gas responds tothe applied thin film magnetic field 162 as shown by the segregation 166of O₂ molecules in the gas sensing cavity 100 (FIG. 11C). Some of the O₂molecules move toward the magnetic north pole, while others move towardthe magnetic south pole, according to the Hall effect. The segregation166 of the O₂ molecules in the thin film magnetic field 162 again tendsto decrease the magnetic field strength, and in turn, the electricpotential difference, across the integrated Hall effect sensor 70 asdetected by the volt meter 116. After a short time interval the voltmeter 116 reads 0.8 mV, indicating development of a Hall voltage 82 of0.2 V across the gas sample which can be related to an oxygenconcentration within the gas sample (FIG. 11C). Like that in theminiature magnetic field-based gas sensor 98, the integrated Hall effectsensor 70 in the alternative oxygen sensor 156 is capable of detecting amomentary magnetic field in the range of a few μTesla. Therefore, thealternative oxygen sensor 156 can also feature a very fast response time(e.g., milliseconds or microseconds), as compared with a macroscopicconventional oxygen detector (e.g., that shown in FIG. 3).

In one embodiment, some or all of the logic circuits that form theop-amp 58 and other logic devices of the sensing circuits are formed inthe same substrate 84 that contains the contact pads 114 and 115. Thisreduces the distance that a signal needs to travel from the analog senselocation 100 to the electrical detection and measurement circuit, whichincludes the op-amp 58 and other circuits. It also reduces the amount ofnoise that can enter the signal prior to being placed in digital form.In such embodiments, the substrate 84 is a monocrystalline substrate inwhich transistors and logic circuits can be formed. In otherembodiments, the substrate 84 is a polycrystalline or amorphoussubstrate. Thus, in one embodiment, the substrate 84 can bepolycrystalline silicon, amorphous silicon, quartz, sapphire, or othersubstrate material.

FIG. 12 shows an exemplary sequence of steps in a fabrication process170 for making a miniature magnetic field-based oxygen sensor.

At 172 a miniature Hall effect sensor (e.g., a sensor resembling theconventional semiconductor-based Hall effect sensor 70) can be definedon the crystalline silicon substrate 84 according to the cross sectionshown in FIG. 5.

At 174, the top metal layer of the Hall effect sensor 70 can bepatterned to provide electrical sensor contact pads 114 and 115 (V₁ andV₂ contacts, respectively), at which a Hall voltage can be measured.

At 176, a metal film (e.g., a chromium-gold (Cr—Au) film) can bedeposited onto the amorphous (e.g., glass) substrate 108 and patternedto form a micro-channel mask. The chromium-gold film may be in the formof a bi-layer wherein the chromium thickness is about 250 nm and thegold thickness is about 5000 nm.

At 178, the amorphous substrate 108 can be etched through themicro-channel mask to form the micro-channel 141 so as to have a channeldepth of about 20 μm.

Once the micro-channel 141 is formed, at 180, the openings 136, 138, and140 can be drilled into the amorphous substrate 108 to provide accessfor ambient air to enter and be maintained at a constant volume in themicro-channel 141. A flow of air is not needed to perform the Halleffect measurements. The area of the openings 136, 138, 140 can be about(100 μm)².

Optionally, at 181, a ferromagnetic film (e.g., an FeCoNi film) can bedeposited and patterned on a surface of the micro-channel 141 to formthe integrated thin film permanent magnet 158. The thin film permanentmagnet 158 is sized and dimensioned to fit, or to define, thegas-sensing cavity 100 for the alternative oxygen sensor 156.

At 182, the amorphous substrate 108 can be bonded to the crystallinesilicon substrate 84 using anodic bonding, metal eutectic bonding, or anadhesive bonding technique. Examples of adhesives that may be used inbonding such substrates include epoxy, or a polyimide film.

At 184, the bonded substrates 108 and 84 can be diced into individualsensor chips.

At 186, the sensor chips can be assembled into an open package. The openpackage may support one or more sensor chips that are stacked with, orplaced adjacent to, other sensor chips and/or integrated circuit chipscarrying signal processing circuitry, microprocessors, electronicmemory, and the like. During a packaging process, the chips may beelectrically coupled to one another by wire bonding.

The various embodiments described above can be combined to providefurther embodiments. All of the U.S. patents, U.S. patent applicationpublications, U.S. patent applications, foreign patents, foreign patentapplications and non-patent publications referred to in thisspecification and/or listed in the Application Data Sheet areincorporated herein by reference, in their entirety. Aspects of theembodiments can be modified, if necessary to employ concepts of thevarious patents, applications and publications to provide yet furtherembodiments

These and other changes can be made to the embodiments in light of theabove-detailed description. In general, in the following claims, theterms used should not be construed to limit the claims to the specificembodiments disclosed in the specification and the claims, but should beconstrued to include all possible embodiments along with the full scopeof equivalents to which such claims are entitled. Accordingly, theclaims are not limited by the disclosure.

The invention claimed is:
 1. A gas micro-sensor comprising: amicro-channel formed within a solid carrier, the micro-channelconfigured to contain a gas sample; a magnet disposed adjacent to themicro-channel and positioned to apply a magnetic field to the gassample; and a semiconductor-based differential Hall effect sensorpositioned adjacent to the micro-channel and responsive to a momentarychange in the magnetic field within the micro-channel.
 2. Themicro-sensor of claim 1 wherein the Hall effect sensor is configured tomeasure a Hall voltage in response to segregation of gas atoms in themagnetic field.
 3. The micro-sensor of claim 1, further comprising areference apparatus in which a Hall voltage is measured and comparedwith a control voltage from an unmagnetized reference sensor.
 4. Themicro-sensor of claim 1 wherein a portion of the micro-channel is agas-sensing cavity containing a paramagnetic gas sample.
 5. Themicro-sensor of claim 1 wherein a strength of the magnetic field iswithin the range of 1-100 μTesla.
 6. The micro-sensor of claim 1 whereinthe solid carrier is made of glass and the micro-sensor furthercomprises a silicon substrate bonded to the glass.
 7. A method ofdetecting a paramagnetic gas, the method comprising: applying a magneticfield to a miniature gas-sensing cavity within a carrier, the miniaturegas-sensing cavity equipped with a miniature Hall effect sensor;introducing a gas sample into the miniature gas-sensing cavity via amicro-channel; and measuring a Hall voltage indicative of a presence ofthe paramagnetic gas in the gas sample.
 8. The method of claim 7 furthercomprising: coupling a miniature reference element to the micro-channelso that the reference element is in fluid communication with theminiature gas-sensing cavity; and comparing the measured Hall voltage toa measured reference voltage of the reference element in which nomagnetic field is applied.
 9. The method of claim 7 wherein theparamagnetic gas is oxygen.
 10. A miniature oxygen detector, comprising:two patterned substrates bonded together to form a micro-channel; apermanent magnet positioned to apply a magnetic field across themicro-channel; and a Hall effect sensor positioned adjacent to themicro-channel.
 11. The detector of claim 10 wherein the permanent magnetis external to the micro-channel.
 12. The detector of claim 10 whereinthe permanent magnet is a magnetic thin film integrated into themicro-channel.
 13. The detector of claim 12 wherein the magnetic thinfilm is made of FeCoNi.
 14. The detector of claim 10 wherein one of thetwo patterned substrates is crystalline and the other of the twopatterned substrates is amorphous.
 15. The detector of claim 10 whereinboth substrates are crystalline.
 16. The detector of claim 10 whereinthe Hall effect sensor is formed in a crystalline silicon substrate.